EP2323755B1 - Verfahren und vorrichtung zur carbonylierung von methanol mit einem mit essigsäure angereicherten flashstrom - Google Patents

Verfahren und vorrichtung zur carbonylierung von methanol mit einem mit essigsäure angereicherten flashstrom Download PDF

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EP2323755B1
EP2323755B1 EP09739136.1A EP09739136A EP2323755B1 EP 2323755 B1 EP2323755 B1 EP 2323755B1 EP 09739136 A EP09739136 A EP 09739136A EP 2323755 B1 EP2323755 B1 EP 2323755B1
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reaction mixture
weight
process according
iodide
carbonylation process
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EP2323755A1 (de
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Jeremy J. Patt
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Celanese International Corp
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Celanese International Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/06—Flash distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J14/00—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor
    • B01J14/005—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/06—Crystallising dishes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C07C51/445—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation by steam distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/08—Acetic acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00164—Controlling or regulating processes controlling the flow
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00191—Control algorithm
    • B01J2219/00193—Sensing a parameter
    • B01J2219/00195—Sensing a parameter of the reaction system
    • B01J2219/00202—Sensing a parameter of the reaction system at the reactor outlet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00191—Control algorithm
    • B01J2219/00211—Control algorithm comparing a sensed parameter with a pre-set value
    • B01J2219/00213—Fixed parameter value
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00191—Control algorithm
    • B01J2219/00222—Control algorithm taking actions
    • B01J2219/00227—Control algorithm taking actions modifying the operating conditions
    • B01J2219/0024—Control algorithm taking actions modifying the operating conditions other than of the reactor or heat exchange system
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—Iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0231—Halogen-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls

Definitions

  • the present invention relates to acetic acid manufacture with improved efficiency provided by way of heating a flash vessel to maintain an elevated flash vapor temperature, generally more than 148.88°C (300°F).
  • an elevated flash vapor temperature generally more than 148.88°C (300°F).
  • a methanol carbonylation production line includes a reactor, a flasher, purification and recycle.
  • methanol and carbon monoxide are contacted with rhodium or iridium catalyst in a homogenous stirred liquid phase reaction medium in a reactor to produce acetic acid.
  • Methanol is pumped to the reactor from a methanol surge tank.
  • the process is highly efficient, having a conversion of methanol to acetic acid of typically greater than 99 percent.
  • a flash vessel coupled to the reactor flashes a draw stream in order to remove crude product from the reaction mixture.
  • the crude product is fed to a purification section which includes generally a light ends or stripper column, a drying column, auxiliary purification and optionally a finishing column.
  • a purification section which includes generally a light ends or stripper column, a drying column, auxiliary purification and optionally a finishing column.
  • various vent streams containing light ends notably methyl iodide, carbon monoxide and methyl acetate are generated and fed to a light ends recovery section. These vent streams are scrubbed with a solvent to remove the light ends which are returned to the system or discarded.
  • EP 0 768 295 discloses use of a flash zone to obtain a feed mixture for a first distillation column in the purification of acetic acid manufactured by methanol carbonylation.
  • a carbonylation process for producing acetic acid comprising: (a) carbonylating methanol or its reactive derivatives in the presence of a Group VIII metal catalyst and methyl iodide promoter to produce a liquid reaction mixture including acetic acid, water, methyl acetate and methyl iodide; (b)feeding the liquid reaction mixture to a flash vessel which is maintained at a reduced pressure; (c) heating the flash vessel while concurrently flashing the reaction mixture to produce a crude product vapor stream, wherein the reaction mixture is selected and the flow rate of the reaction mixture to the flash vessel as well as the amount of heat supplied to the flash vessel is controlled such that the temperature of the crude product vapor stream is maintained at a temperature of greater than 148.88°C (300°F) as measured at a vapor outlet of the flash vessel and the concentration of acetic acid in the crude product vapor stream is greater than 70% by weight of the stream.
  • Reduced pressure refers to a pressure less than that of the reactor vessel.
  • a "like" stream undergoing flashing refers to a feed stream of the same composition which yields a product stream having the same flow rate of acetic acid in the flash vapor. See Tables 1-7.
  • the feed temperature of the reaction mixture to the flasher is measured as close as practical to the inlet of the flasher, on the high pressure side. Any suitable instrumentation may be used.
  • the temperature of the crude product vapor stream is measured as close as practical to the vapor outlet of the flasher vessel.
  • a Group VIII catalyst metal used in connection with the present invention may be a rhodium and/or iridium catalyst.
  • the rhodium metal catalyst may be added in any suitable form such that rhodium is in the catalyst solution as an equilibrium mixture including [Rh(CO) 2 I 2 ] - anion as is well known in the art.
  • solubility of the rhodium is generally maintained because rhodium/carbonyl iodide anionic species are generally soluble in water and acetic acid.
  • Rhodium precipitates as RhI 3 for example; details as to the form of entrained rhodium downstream of the reactor is not well understood.
  • Iodide salts help alleviate precipitation in the flasher under so-called "low water” conditions as will be appreciated by one of skill in the art.
  • Iodide salts maintained in the reaction mixtures of the processes described herein may be in the form of a soluble salt of an alkali metal or alkaline earth metal or a quaternary ammonium or phosphonium salt.
  • the catalyst co-promoter is lithium iodide, lithium acetate, or mixtures thereof.
  • the salt co-promoter may be added as a non-iodide salt or ligand that will generate an iodide salt.
  • the iodide catalyst stabilizer may be introduced directly into the reaction system.
  • the iodide salt may be generated in-situ since under the operating conditions of the reaction system, a wide range of non-iodide salt precursors will react with methyl iodide to generate the corresponding co-promoter iodide salt stabilizer.
  • iodide salt generation see U.S. Patents 5,001,259 to Smith et al .; 5,026,908 to Smith et al .; and 5,144,068, also to Smith et al. .
  • the iodide salt may be added as a phosphine oxide or any organic ligand, if so desired. These compounds and other ligands generally undergo quaternization in the presence of methyl iodide at elevated temperatures to yield suitable salts which maintain iodide anion concentration.
  • An iridium catalyst in the liquid carbonylation reaction composition may comprise any iridium-containing compound which is soluble in the liquid reaction composition.
  • the iridium catalyst may be added to the liquid reaction composition for the carbonylation reaction in any suitable form which dissolves in the liquid reaction composition or is convertible to a soluble form.
  • Chloride-free complexes of iridium such as acetates, oxalates and acetoacetates are usually employed as starting materials.
  • the iridium catalyst concentration in the liquid reaction composition may be in the range of 100 to 6000 ppm.
  • the carbonylation of methanol utilizing iridium catalyst is well known and is generally described in the following United States Patents: 5,942,460 ; 5,932,764 ; 5,883,295 ; 5,877,348 ; 5,877,347 and 5,696,284 .
  • Methyl iodide is used as the promoter.
  • concentration of methyl in the liquid reaction composition is in the range 1 to 50% by weight, preferably 2 to 30% by weight.
  • the promoter may be combined with a salt stabilizer/co-promoter compound, which may include salts of a metal of Group IA or Group IIA, or a quaternary ammonium or phosphonium salt. Particularly preferred are iodide or acetate salts, e . g ., lithium iodide or lithium acetate.
  • promoters and co-promoters may be used as part of the catalytic system of the present invention as described in European Patent Publication EP 0 849 248 .
  • Suitable promoters are selected from ruthenium, osmium, tungsten, rhenium, zinc, cadmium, indium, gallium, mercury, nickel, platinum, vanadium, titanium, copper, aluminum, tin, antimony, and are more preferably selected from ruthenium and osmium.
  • Specific co-promoters are described in United States Patent No. 6,627,770 .
  • a promoter may be present in an effective amount up to the limit of its solubility in the liquid reaction composition and/or any liquid process streams recycled to the carbonylation reactor from the acetic acid recovery stage.
  • the promoter is suitably present in the liquid reaction composition at a molar ratio of promoter to metal catalyst of [0.5 to 15]:1, preferably [2 to 10]:1, more preferably [2 to 7.5]:1.
  • a suitable promoter concentration is 400 to 5000 ppm.
  • the present invention may be appreciated in connection with, for example, the carbonylation of methanol with carbon monoxide in a homogeneous catalytic reaction system comprising a reaction solvent (typically acetic acid), methanol and/or its reactive derivatives, a soluble rhodium catalyst, at least a finite concentration of water.
  • a reaction solvent typically acetic acid
  • methanol and/or its reactive derivatives typically a soluble rhodium catalyst
  • the carbonylation reaction proceeds as methanol and carbon monoxide are continuously fed to the reactor.
  • the carbon monoxide reactant may be essentially pure or may contain inert impurities such as carbon dioxide, methane, nitrogen, noble gases, water and C 1 to C 4 paraffmic hydrocarbons.
  • the presence of hydrogen in the carbon monoxide and generated in situ by the water gas shift reaction is preferably kept low, for example, less than 1 Bar partial pressure, as its presence may result in the formation of hydrogenation products.
  • the partial pressure of carbon monoxide in the reaction is suitably in the range 1 to 70 bar, preferably 1 to 35 bar, and most preferably 1 to 15 bar.
  • the pressure of the carbonylation reaction is suitably in the range 10 to 200 Bar, preferably 10 to 100 bar, most preferably 15 to 50 Bar.
  • the temperature of the carbonylation reaction is suitably in the range 100 to 300°C, preferably in the range 150 to 220°C.
  • Acetic acid is typically manufactured in a liquid phase reaction at a temperature of from about 150 - 200°C and a total pressure of from about 20 to about 50 bar.
  • Acetic acid is typically included in the reaction mixture as the solvent for the reaction.
  • Suitable reactive derivatives of methanol include methyl acetate, dimethyl ether, methyl formate and methyl iodide.
  • a mixture of methanol and reactive derivatives thereof may be used as reactants in the process of the present invention.
  • methanol and/or methyl acetate are used as reactants.
  • At least some of the methanol and/or reactive derivative thereof will be converted to, and hence present as, methyl acetate in the liquid reaction composition by reaction with acetic acid product or solvent.
  • the concentration in the liquid reaction composition of methyl acetate is suitably in the range 0.5 to 70% by weight, preferably 0.5 to 50% by weight, more preferably 1 to 35% by weight and most preferably 1-20% by weight.
  • Water may be formed in situ in the liquid reaction composition, for example, by the esterification reaction between methanol reactant and acetic acid product. Water may be introduced to the carbonylation reactor together with or separately from other components of the liquid reaction composition. Water may be separated from other components of reaction composition withdrawn from the reactor and may be recycled in controlled amounts to maintain the required concentration of water in the liquid reaction composition. Preferably, the concentration of water maintained in the liquid reaction composition is in the range 0.1 to 16% by weight, more preferably 1 to 14% by weight, most preferably 1 to 10% by weight.
  • the reaction liquid is typically drawn from the reactor and flashed in a one step or multi-step process using a converter as well as a flash vessel as hereinafter described.
  • the crude vapor process stream from the flasher is sent to a purification system which generally includes at least a light ends column and a dehydration column.
  • FIG. 1 is a schematic diagram illustrating a typical carbonylation process and apparatus.
  • a carbonylation system 10 including a reactor 12 provided with a feed system 14 including a methanol surge tank 16 and carbon monoxide feed line 18 .
  • a catalyst reservoir system includes a methyl iodide storage vessel 20 as well as a catalyst storage tank 22 .
  • Reactor 12 is provided with a vent 24 and an optional vent 24a .
  • Reactor 12 is coupled to a flash vessel 26 by way of a conduit 28 and optionally by way of vent 24a .
  • the flasher is coupled to a purification section 30 which includes a light ends or stripper column 32 , a dehydration column 34 and a strong acid, silver-exchanged cation ion-exchange resin bed 36 which removes iodides from the product.
  • a purification section 30 which includes a light ends or stripper column 32 , a dehydration column 34 and a strong acid, silver-exchanged cation ion-exchange resin bed 36 which removes iodides from the product.
  • a silver-exchanged, strong acid cation ion-exchange resin it has been reported that anion ion-exchange resin can be used to remove iodides. See British Patent No. G 2112394A , as well as United States Patent No. 5,416,237 , Col. 7, lines 54+, which teaches the use of 4-vinylpyridine resins for iodide removal.
  • a gaseous purge stream is typically vented from the head of the reactor to prevent buildup of gaseous by-products such as methane, carbon dioxide and hydrogen and to maintain a set carbon monoxide partial pressure at a given total reactor pressure.
  • gaseous by-products such as methane, carbon dioxide and hydrogen
  • a so-called "converter" reactor can be employed which is located between the reactor and flasher vessel shown in Figure 1 and discussed further in connection with Figure 2 .
  • the gaseous purge streams may be vented through the flasher base liquid or lower part of the light ends column to enhance rhodium stability and/or they may be combined with other gaseous process vents (such as the purification column overhead receiver vents) prior to scrubbing.
  • Carbon monoxide and methanol are introduced continuously into reactor 12 with adequate mixing at a high carbon monoxide partial pressure.
  • the non-condensable bi-products are vented from the reactor to maintain an optimum carbon monoxide partial pressure.
  • the reactor off gas is treated to recover reactor condensables, i.e., methyl iodide before flaring.
  • Methanol and carbon monoxide efficiencies are generally greater than about 98 and 90% respectively.
  • major inefficiencies of the process are the concurrent manufacture of carbon dioxide and hydrogen by way of the water gas shift reaction.
  • a stream of the reaction mixture is continuously fed via conduit 28 to flasher 26 .
  • the product acetic acid and the majority of the light ends (methyl iodide, methyl acetate, and water) are separated from the reactor catalyst solution, and the crude process stream 38 is forwarded with dissolved gases to the distillation or purification section 30 in single stage flash.
  • the catalyst solution is recycled to the reactor via conduit 40 .
  • the flasher is heated with steam, for example, by way of jacketing or coils in order to raise the temperature of stream 38 .
  • Alternative heating means such as electric heating or radiant (microwave) heating can be used if more convenient.
  • the purification of the acetic acid typically includes distillation in a light ends column, a dehydration column, and, optionally, a heavy ends column.
  • the crude vapor process stream 38 from the flasher is fed into the light ends column 32 .
  • a liquid recycle stream 45 from the light ends column may also be returned to the reactor.
  • the purified process stream 50 is drawn off the side of the light ends column 32 and is fed into dehydration column 34 . Water and some acetic acid from this column separate and are recycled to the reaction system via recycle line 44 as shown.
  • the purified and dried process stream 52 from the dehydration column 34 feeds resin bed 36 and product is taken therefrom at 56 as shown.
  • Carbonylation system 10 uses only two primary purification columns and is preferably operated as described in more detail in United States Patent No. 6,657,078 to Scates et al. , entitled "Low Energy Carbonylation Process". Additional columns are generally used as desired, depending on the system.
  • FIG. 2 An alternate layout of the reactor/flasher with a converter vessel 12a therebetween as well as a heat exchanger 60 and a low pressure steam flash vessel 62 .
  • Reactor 12 and flasher 26 operate as described above. Methanol and carbon monoxide are provided to reactor 12 at 18a , 18 and liquid reaction mixture is drawn at 28a and provided to converter vessel 12a which vents gas including light ends to a scrubber (not shown). The vent gas can be scrubbed with methanol and returned to the reactor.
  • Converter 12a feeds flasher 26 where the pressure is reduced and flashed to crude product stream 38 .
  • Recycle to the reactor is provided by way of lines 40 , 44 as is discussed above in connection with Figure 1 .
  • Flasher 26 is heated by way of a low pressure steam supply 64 provided from a steam flash vessel 62 which is fed from heat exchanger 60 .
  • Heat exchanger 64 is made with suitable metallurgy and receives hot catalytic mixture from reactor 12 via line 66 as well as steam condensate via line 68 .
  • the condensate is heated by the hot catalyst which, in turn, requires cooling because of the exothermic nature of the carbonylation reaction.
  • the heated condensate is supplied to vessel 62 via line 70 where it is flashed to (low pressure) steam and used to heat flasher 26 as noted above.
  • heat exchanger 64 as shown in Figure 2 provides cooling to the reactor and heat to the flasher which reduces overall energy costs as will be appreciated by one of skill in the art.
  • Carbon monoxide may be added directly to converter 12a if so desired or may be added slightly before (upstream) or after (downstream) if so desired in order to stabilize the catalyst solution and consume any unreacted methanol. Details of such arrangements are seen in European Patent No. EP 0 759 419 as well as United States Patent No. 5,770, 768 to Denis et al. .
  • the present invention substantially increases the efficiency of the system by providing a higher concentration of acetic acid in the crude product vapor stream as will be appreciated form the discussion which follows.
  • the carbonylation apparatus shown in Figure 1 and that illustrated in Figure 2 can be represented schematically as shown in Figure 3 for present purposes.
  • the feed to the reactor is designated stream 1
  • the liquid stream to the flasher is designated stream 2
  • the crude product vapor stream provided to the splitter column is designated stream 3
  • the purified product stream is labeled stream 4.
  • Stream 5 represents the catalyst recycle stream from the flasher and stream 6 represents recycle from purification recycle to the reactor.
  • Figure 3 illustrates two major inefficiencies of the methanol carbonylation process generally; catalyst recycle (5) and purification recycle (6). Both of these internal 'flywheels' are energy and capital-intensive and could be minimized by improving performance of the flasher - by ensuring that the vapor stream that it sends to purification (3) has proportionally more HAc and less "non-product" components (H 2 O, MeAc, MeI). This can be accomplished by providing heat input to raise the operating temperature of the flasher.
  • HAc HAc and less "non-product” components
  • a semi-empirical simulator was used to study the effect of flash temperature while holding constant the mass flow of HAc in the vapor stream (3).
  • the stream compositions are shown below for vapor (3) and liquid (5) exiting the flasher.
  • the flasher inlet basis is a stream at 197.22°C (387°F), 2757.9 kPa gauge (400 psig), containing 8.1 wt% MeI, 2.9 wt% MeAc, 75.7 wt% HAc, 2.8 wt% H 2 O, and 10.6 wt% LiI.
  • Flash temperature (temperature of the vapor stream) was varied from adiabatic (147.22°C (297°F)) to isothermal (197.22°C (387°F)), all cases to 172.37 kPa gauge (25 psig).
  • Figure 6 shows the effect of flasher temperature on the mass flow rate of each component in the vapor stream that is fed to purification (3). It shows that for a set amount of HAc throughput, smaller quantities of the "non-product" components are sent to purification when using a higher flash temperature. For example, raising the flash temperature from 147.22 to 154.44°C (297 to 310°F) would decrease the mass flow of water sent to purification by 30%, MeAc by 55% and MeI by 55%.
  • Benefits include: (1) for an existing unit, increasing HAc in the crude product stream, thus debottlenecking purification and lower operating costs and/or allow an increase in capacity; (2) running the reactor at higher MeAc, currently this level is typically constrained by purification capacity, higher MeAc also allows the reactor to operate at a lower temperature and also decreases the make rate of propionic acid; (3) for a new unit, the capital and energy requirements are reduced by requiring less catalyst recycle and purification throughput for a given production rate of HAc; (4) decrease in vapor feed rate to purification reduces catalyst loss via entrainment; and (5) decrease in liquid feed rate to the flasher improves CO efficiency by significantly reducing the carryover loss of soluble CO (which currently accounts for 80% of the total CO waste).

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Claims (10)

  1. Carbonylierungsverfahren zum Herstellen von Essigsäure, umfassend:
    a) Carbonylieren von Methanol oder seinen reaktiven Derivaten in Gegenwart von einem Gruppe VIII-Metallkatalysator und einem Methyliodidpromotor, um eine flüssige Reaktionsmischung herzustellen, die Essigsäure, Wasser, Methylacetat und Methyliodid umfasst;
    b) Zuführen von der flüssigen Reaktionsmischung zu einem Entspannungsgefäß, das auf einem verringerten Druck gehalten wird;
    c) Erhitzen von dem Entspannungsgefäß, während gleichzeitig die Reaktionsmischung entspannt wird, um einen Rohproduktdampfstrom herzustellen,
    wobei die Reaktionsmischung ausgewählt wird und die Strömungsrate von der Reaktionsmischung zu dem Entspannungsgefäß als auch die Menge der Wärme, die dem Entspannungsgefäß zugeführt wird, so gesteuert werden, dass die Temperatur von dem Rohproduktdampfstrom auf einer Temperatur von mehr als 148,88 °C (300 °F) gehalten wird, gemessen an einem Dampfauslass des Entspannungsgefäßes, und die Konzentration der Essigsäure in dem Rohproduktdampfstrom mehr als 70 Gew.-% von dem Dampfstrom beträgt.
  2. Carbonylierungsverfahren nach Anspruch 1, wobei die Menge des Wassers in der Reaktionsmischung auf einem Niveau von 1 Gew.-% bis 10 Gew.-% von der Reaktionsmischung gehalten wird und die Reaktionsmischung ferner einen Iodidsalz-Copromotor umfasst.
  3. Carbonylierungsverfahren nach Anspruch 2, wobei der lodidsalz-Copromotor mit einer Menge vorliegt, die eine Iodidanionenkonzentration von 4 Gew.-% bis 20 Gew.-% von der Reaktionsmischung erzeugt.
  4. Carbonylierungsverfahren nach Anspruch 2, wobei der lodidsalz-Copromotor eine Mischung aus Iodidsalzen ist.
  5. Carbonylierungsverfahren nach Anspruch 2, wobei der Iodidsalz-Copromotor der Reaktionsmischung in der Form von einem Iodidligandenvorläufer bereitgestellt wird.
  6. Carbonylierungsverfahren nach Anspruch 3, wobei die Menge des Wassers in der Reaktionsmischung auf einem Niveau von 1 Gew.-% bis 5 Gew.-% von der Reaktionsmischung gehalten wird.
  7. Carbonylierungsverfahren nach Anspruch 1, wobei der Gruppe VIII-Metallkatalysator aus Rhodiumkatalysatoren und Iridiumkatalysatoren ausgewählt ist.
  8. Carbonylierungsverfahren nach Anspruch 1, wobei der Gruppe VIII-Metallkatalysator ein Rhodiumkatalysator ist und in der Reaktionsmischung mit einer Konzentration von 300 ppm bis 5000 ppm bezogen auf das Gewicht der Reaktionsmischung vorliegt.
  9. Carbonylierungsverfahren nach Anspruch 1, wobei die Carbonylierung unter einem Manometerdruck von 10 bis 100 bar durchgeführt wird.
  10. Carbonylierungsverfahren nach Anspruch 1, wobei das Entspannungsgefäß auf einem Manometerdruck von 0,25 bis 3 bar gehalten wird.
EP09739136.1A 2008-04-29 2009-04-23 Verfahren und vorrichtung zur carbonylierung von methanol mit einem mit essigsäure angereicherten flashstrom Active EP2323755B1 (de)

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US20150175516A1 (en) 2015-06-25
US10118885B2 (en) 2018-11-06
US20090270650A1 (en) 2009-10-29
ZA201007491B (en) 2012-01-25
US20140323760A1 (en) 2014-10-30
EP3002057B1 (de) 2018-10-24
WO2009134333A1 (en) 2009-11-05
MX338852B (es) 2016-05-02
BRPI0911487A2 (pt) 2016-01-05
US9840451B2 (en) 2017-12-12
US7820855B2 (en) 2010-10-26
RU2010148399A (ru) 2012-06-10
ZA201102114B (en) 2012-01-25
MX2010011852A (es) 2010-12-02
US10519089B2 (en) 2019-12-31
DE09739136T1 (de) 2012-01-19
CN102015088A (zh) 2011-04-13
TW200946493A (en) 2009-11-16
AU2009241844A1 (en) 2009-11-05
CL2009001003A1 (es) 2010-06-04
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NZ588701A (en) 2012-03-30
US8329944B2 (en) 2012-12-11
EP3002057A1 (de) 2016-04-06
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MX364125B (es) 2019-04-12
US20110021817A1 (en) 2011-01-27
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US20130058842A1 (en) 2013-03-07
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US20180065911A1 (en) 2018-03-08
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US8987512B2 (en) 2015-03-24
KR20110003555A (ko) 2011-01-12
US8771616B2 (en) 2014-07-08
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